Bisphenols and poly(imidoarylether ketone)s and poly(imidoarylether sulfone)s produced therefrom

ABSTRACT

Bisphenols having a pendent imide moiety, of formula (I) ##STR1## in which R 1 , R 2 , R 3  and R 4 , which may be the same or different, are selected from hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, alkoxy of 1 to 6 carbon atoms and aryloxy of 6 to 10 carbon atoms; R 5  is selected from fluorine, chlorine, bromine and alkyl of 1 to 6 carbon atoms, and m is 0, 1, 2, 3 or 4; and R 7  is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, unsubstituted or substituted one or more times by a substituent selected from fluorine, chlorine, trifluoromethyl, alkyl of 1 to 6 carbon atoms, and phenyl, or heteroaryl; are useful in producing poly(imidoarylether ketone)s and poly(-imidoarylether sulfone)s which are amorphous and are soluble in readily available solvents, while displaying high glass transition temperatures and good thermo-oxidative stability.

This is a continuation of application Ser. No. 07/704,930, filed May 23, 1991, now U.S. Pat. No. 5,110,934.

BACKGROUND OF THE INVENTION

i) Field of the Invention

This invention relates to novel bisphenols having a pendent imide moiety and their preparation, and to poly(imidoarylether) ketones and sulfones produced from the novel bisphenols.

ii) Background of the Invention

Polyimides are synthesized by the reaction of a diamine with a dianhydride, typically this is a two-step reaction route because of the insolubility and infusibility of the resulting polyimide. In the reaction a polyamic acid is formed which is thermally ring-closed to produce the polyimide. Takekoshi T. in Polymer Journal, 1987, 19, 191, describes polyetherimides which overcome these difficulties by using bisphenols such as 4,4'-(1-methylethylidene)bisphenol which introduces flexibility into the polymer chain and provides polymers which are melt processable.

There exists a need for polymers which are soluble in readily available organic solvents and that have high glass transition temperatures and thermo-oxidative stability.

SUMMARY OF THE INVENTION

It is an object of this invention to provide novel bisphenols and their preparation, which bisphenols are useful in preparing novel poly(imidoarylether) ketones, and poly(imidoarylether) sulfones.

It is a further object of this invention to provide novel poly(imidoarylether ketone)s and poly(imidoarylether sulfone)s, and their preparation, which have high glass transition temperatures, are thermo-oxidatively stable, and are soluble in organic solvents. ##STR2## in which R₁, R₂, R₃ and R₄, which may be the same or different, are selected from hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, alkoxy of 1 to 6 carbon atoms and aryloxy of 6 to 10 carbon atoms; R₅ is selected from fluorine, chlorine, bromine and alkyl of 1 to 6 carbon atoms and m is 0, 1, 2, 3 or 4; and R₇ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, unsubstituted or substituted one or more times by a substituent selected from fluorine, chlorine, trifluoromethyl, alkyl of 1 to 6 carbon atoms, and phenyl, or heteroaryl.

In accordance with another aspect of the invention there is provided a process for preparing the bisphenols (I).

In still another aspect of the invention there is provided a polymer of formula (II): ##STR3## in which R₁, R₂, R₃, R₄, R₅, R₇ and m are as defined above; X is --CO--, --SO₂ -- or --CO--Ar--CO-- in which Ar is phenylene; and n is an integer of 2 to 200.

In still another aspect of the invention there is provided a process for preparing the polymers (II).

DESCRIPTION OF PREFERRED EMBODIMENTS

i) Bisphenols

The preferred bisphenols (I) are those in which m is 0 such that the benzene ring is unsubstituted and R₁, R₂, R₃ and R₄ are all hydrogen. These preferred bisphenols can be produced from phenolphthalein which is readily available.

It is also preferred that R₁ and R₃ be the same, and that R₂ and R₄ be the same. The aryl radical and the aryl moiety in the definition of R₁, R₂, R₃, R₄ and R₇ is preferably phenyl or naphthyl.

The heteroaryl in the definition of R₇ is, in particular, pyridinyl or quinolinyl.

When R₇ is dodecyl the bisphenol (I) is readily soluble in N-methylpyrrolidone (NMP) at 25° C., while when R₇ is phenyl or methyl, moderate temperatures are required to give homogeneous solutions. These temperatures were 60° C. and 80° C., respectively, for the preferred subclass described above.

ii) Preparation of Bisphenols

The preparation of the bisphenols is illustrated in Scheme 1 below for the preferred case in which R₁, R₂, R₃ and R₄ are all hydrogen and m is 0. In such case, the reaction scheme as illustrated commences with phenolphthalein (III) which is readily available. ##STR4##

The overall process commencing with phenolphthalein may be considered a three-step sequence rather than a four-step sequence, since the last two steps can be carried out in one pot.

In Scheme 1 the phenolphthalein (III) is reduced to phenolphthalin (IV) employing the procedure of Blicke, F. F.; Patelski, R. A., in J. Am. Chem. Soc., 1936, 58, 274, with zinc and sodium hydroxide in aqueous ethanol under reflux. This reaction proceeds efficiently to yields in excess of 95%. The phenolphthalin (IV) is rearranged in concentrated sulfuric acid to the isobenzofuran (V) using a modified procedure of Blicke and Weinkauf, J. Am. Chem. Soc., 1934, 54, 1454.

The isobenzofuran (V) is reacted with a maleimide (VI) under Diels-Alder conditions, typically in ethanol at moderate elevated temperatures, for example about 60° C.; and the reaction product (VII) is dehydrated, for example with gaseous hydrogen chloride at a temperature of 70-80° C. to produce the bisphenol (I).

In the general reaction the phenolphthalein (III) is replaced by a compound of formula (VIII): ##STR5## in which R₁, R₂, R₃, R₄, R₅ and m are as defined above, and is reduced to a compound of formula (IX): ##STR6## in which R₁ to R₅ and m are as defined above.

Thus the process of the invention contemplates reacting a compound of formula (X): ##STR7## in which R₁, R₂, R₃, R₄, R₅ and m are as defined above, with the maleimide (VI) as defined above and dehydrating the Diels-Alder adduct (XI): ##STR8## in which R₁, R₂, R₃, R₄, R₅, R₇ and m are as defined above to produce the bisphenol (I).

iii) Polymer Synthesis

The polymerization of the bisphenols (I) to produce the polymers (II) is illustrated in Scheme 2 below for the preferred case in which R₁, R₂, R₃ and R₄ are all hydrogen, and m is 0. The polymerization is suitably carried out with 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone or 1,3-bis-(4-halobenzoyl)benzene in which the halo is fluoro or chloro, preferably fluoro. The polymerization is suitably carried out in a solvent, for example N-methylpyrrolidone, dimethylsulfoxide or sulfolane, in the presence of an excess of anhydrous potassium carbonate; the choice of solvent depends on the solubility characteristics of the resulting polymers and appropriate solvents can readily be determined by routine experiments. ##STR9##

Furthermore, when R₇ is methyl, high molecular weight polymers can not be synthesized with difluorobenzophenone and difluorodiphenylsulfone when the solvent is N-methylpyrrolidone because oligomers rapidly precipitate from the reaction solution during the polymerization. High molecular weight polymers can be synthesized when sulfolane is the solvent.

The integer n is a measure of the degree of polymerization and usually will be in the preferred range of 100 to 150.

iv) Polymers

Depending on the value of X the polymers of the invention are characterized as poly(imidoarylether ketone)s or poly(imidoarylether sulfone)s.

In agreement with the solubility characteristics of the parent bisphenols (I), the R₇ group has a dramatic effect on the solubility of the resulting polymer.

When R₇ is dodecyl, for example, all the polymers are amorphous and readily soluble in chloroform and methylene chloride at room temperature. On the other hand when R₇ is, for example, phenyl or methyl, the polymers are less soluble in chloroform and the poly(imidoarylether ketone)s dissolve only in certain dipolar aprotic solvents.

Table 1 below provides a compilation of chemical properties and solubilities of polymers (II) for different values of R₇ for the preferred case in which R₁, R₂, R₃ and R₄ are all hydrogen and m is 0.

                                      TABLE 1                                      __________________________________________________________________________     THERMAL PROPERTIES OF POLYMERS                                                              Polymerization                                                                               TGA (C.)**                                          R.sub.7                                                                             Ar      Solvent Tg (C.)*                                                                             air                                                                               N2  Solubility                                   __________________________________________________________________________     Methyl                                                                              Benzophenone                                                                           Sulfolane                                                                                283***                                                                             525                                                                               516 Sulfolane                                         Diphenyl                                                                               Sulfolane                                                                              314   503                                                                               506 CHCl.sub.3 and TCE                                Sulfone                                                                        1,3-Dibenzoyl                                                                          NMP     251   524                                                                               515 CHCl.sub.3                                        benzene                                                                   Dodecyl                                                                             Benzophenone                                                                           NMP     147   482                                                                               491 CHCl.sub.3 /CH.sub.2 CL.sub.2                     Diphenyl                                                                               NMP     167   471                                                                               471 CHCl.sub.3 /CH.sub.2 CL.sub.2                     Sulfone                                                                        1,3-Dibenzoyl                                                                          NMP     140   489                                                                               487 CHCl.sub.3 /CH.sub.2 CL.sub.2                     benzene                                                                   Phenyl                                                                              Benzophenone                                                                           DMSO    275   551                                                                               561 CHCl.sub.3                                        Diphenyl                                                                               NMP     310   556                                                                               550 CHCl.sub.3 (hot)                                  Sulfone                                                                        1,3-Dibenzoyl                                                                          NMP     245   568                                                                               566 CHCl.sub.3 /CH.sub.2 CL.sub.2                     benzene                                                                   __________________________________________________________________________      *DSC. Heating rate 10° C./min                                           **TGA. Heating rate 10° C./min. Values correspond to the                temperature at which a 10% weight loss occurs                                  ***Low molecular weight                                                  

With reference to Table 1, it can be seen that the highest glass transition temperatures Tg are obtained for polymers in which R₇ is methyl, presumably because the polymer chain is most rigid when R₇ is methyl. When R₇ is phenyl, the Tg's are very close to those when R₇ is methyl and the solubility of the polymers is much improved.

When R₇ is dodecyl the Tg's are much lower, and in such case the long alkyl chain R₇ likely functions as an internal plasticizer.

For a given R₇ the poly(imidoarylether sulfone)s have the highest Tg, while the poly(imidoarylether bisketone)s exhibit the lowest Tg.

All of the polymers were amorphous. Attempts were made to induce some degree of crystallinity by holding the ketone polymers in which R₇ was phenyl and dodecyl, for 5 hours above their respective Tg's, followed by cooling to 25° C. Subsequent heating to 300° C. for the polymer in which R₇ is dodecyl, and 400° C. for the polymer in which R₇ is phenyl, failed to reveal a melting point Tm for either polymer.

The polymers in which R₇ is phenyl displayed the highest thermo-oxidative stability while those in which R₇ is methyl and dodecyl are lower by 45-65° C. and 90-100° C., respectively.

Table 2 below identifies the inherent viscosities, molecular weights obtained by gel permeation chromatography using polystyrene standards, and the film color and characteristics of the preferred class of polymers of Table 1.

                                      TABLE 2                                      __________________________________________________________________________     POLYMER VISCOSITIES AND SOLUTION PROPERTIES                                                 Inherent      Solvent for                                                                             GPC***                                     R.sub.7                                                                             Ar      Viscosity*                                                                           Film Color                                                                             Solution Casting                                                                        Mw × 10.sup.5                                                                  M × 10.sup.5                                                                   P.D.                           __________________________________________________________________________     Methyl                                                                              Benzophenone                                                                           --    --      --       --    --    --                                  Diphenyl                                                                                0.64**                                                                              Clear and                                                                              TCE      40    16    2.5                                 Sulfone       Colourless                                                       1,3-Dibenzoyl                                                                          0.62  Tan     CHCl.sub.3                                                                              48    20    2.4                                 benzene                                                                   Phenyl                                                                              Benzophenone                                                                           0.52  Light Brown                                                                            NMP      --    --    --                                  Diphenyl                                                                               0.91  Tan     NMP      90    31    2.9                                 Sulfone                                                                        1,3-Dibenzoyl                                                                          1.24  Clear and Light                                                                        CH.sub.2 Cl.sub.2                                                                       192   62    3.1                                 benzene       Gold                                                        Dodecyl                                                                             Benzophenone                                                                           1.1   Clear and Light                                                                        CH.sub.2 Cl.sub.2                                                                       88    29    3.1                                               Yellow                                                           Diphenyl                                                                               0.55  Clear and                                                                              CH.sub.2 Cl.sub.2                                                                       53    22    2.4                                 Sulfone       Colourless                                                       1,3-Dibenzoyl                                                                          0.9   Clear and                                                                              CH.sub.2 Cl.sub.2                                                                       118   48    2.5                                 benzene       Colourless                                                  __________________________________________________________________________      *NMP at 60.7° C.                                                        **TCE at 25.1° C.                                                       ***Based on Polystyrene Standards                                        

All of the polymers in Table 2 except the ketone polymer in which R₇ is methyl are of high molecular weight and produce tough, flexible films which withstand two 180 degree folds.

Comparing the poly(imidoarylether sulfone) (I) in which R₇ is phenyl and R₁ to R₆ have he preferred values of Tables 1 and 2, with a comparison poly(arylether sulfone) produced with 4,4'-biophenol as the bisphenol, it is found that the polymer of the invention has a glass transition temperature of about 80° C. higher than the Tg of 230° C. of the comparison polymer, and additionally has a higher thermooxidative stability suffering a 10% reduction in weight when heated at a rate of 10° C./min. to a temperature of 550° C. as compared with 530° C. for the comparison polymer.

EXAMPLES Synthesis of Maleimides ##STR10## Procedure A. Two Step Synthesis Example 1.

N-Dodecylmaleimic acid. To a 1000 mL beaker containing 37.8 g (0.204 mol) of dodecylamine in 150 mL of cyclohexane was added 20 g (0.204 mol) of maleic anhydride. The mixture was warmed to 60° C. to dissolve all of the solids and 2 drops of conc. sulfuric acid was added. After 2 hrs. the mixture had deposited a fine white precipitate which was filtered, washed with petroleum ether (50 mL×5), and dried by suction. Yield=98%. m.p.=92° C.

N-Dodecylmalemide. 70.8 g (0.25 mol) of the amic aid was added to a dry 1L round bottom flask containing 600 mL of methyl ethyl ketone (MEK). 52.2 mL (0.375 mol) of dry triethylamine was added dropwise (N.B. most of the amic acid dissolves when the amine is added). 35.4 mL (0.375 mol) of acetic anhydride was added slowly in a dropwise manner while the temperature was increased to 60° C. After 22 hrs. the temperature was reduced to 23° C., and the contents were poured into 2 L of water this was stirred overnight, filtered and dried by suction leaving a tan solid. Weight 66.8 g. Yield=96%. m.p.=47-51° C. This was used without further purification.

Procedure B. One Step Synthesis

Synthesis of Maleimides with substituents on the pendent phenyl group. These maleimides were synthesized in one pot by reacting the appropriate amine with amaleic anhydride in adipolar aprotic solvent (NMP, DMAc, or DMF) to form the amic acid, which was further dehydrated using a catalytic amount of Ni(OAc(2-H2O or NaOAc and acetic anhydride. For N-(4-t-Butyl)pehnyl maleimide, N-(4-chloro)phenyl maleimide, N-(2-Fluoro)phenyl maleimide, N-(4-Fluoro)phenyl maleimide, N-(2-Phenyl)phenyl maleimide, N-(2-trifluoromethyl)phenyl maleimide, and N-(4-trifluoromethyl)phenyl maleimide the following general procedure was used:

To a dry 500 mL round bottom blask at 0° C. containing 0.168 mol of the aniline and 100 mL dry dipolar aprotic solvent (DMAc or NMP) was added 0.168 mol of maleic anhydride all at once. After 5 min. an additional 45 mL of NMP was added. The contents were stirred at 0° C. for about 1 hour and then allowed to warm to room temperature. After 3 hrs. 0.216 g of Ni(OAc)₂.H₂ O and 0.575 mol. of acetic anhydride were added. The mixture was normally stirred for 24-48 hours, and then passed through a 0.5 cm plug of alumina into 1L of H₂ O. If the solids precipitated they were filtered and dried by suction. If the solids did not precipitate, the organic layer was extracted with a suitable solvent (100 mL×5), the combined extracts were washed with brine (200 mL×2), H₂ O (200 mL×2), dried over MgSO4 and conc. in vacuo. If DMAc remained it was removed by distillation under reduced pressure. N-(2-Fluoro)phenyl maleimide, N-(4-Fluoro)phenyl maleimide, N-(4-chlorophenyl)maleimide, and N-(4-trifluoromethyl)phenyl maleimide precipitate when poured into water. N-(2)-Phenyl)phenyl maleimide, and N-(2-trifluoromethyl)phenyl maleimide were extracted from the reaction mixture with EtOAc an EtOEt, respectively. The solids were purified by flash column chromatography through silica gel using petroleum ether: EtOAc (3:1) and petroleum ether/EtOEt (4:1), respectively. For N-(3-trifluoromethyl)phenyl maleimide the same conditions as above were applied except dry DMF was used as solvent, and a catalytic amount of fused NaOAc and 1.4 equiv. of acetic anhydride were used. CHCl3 was used to extract the organic layer. Purification was achieved by flash column chromatography (Pet. eter :EtOAc, 8:1).

    __________________________________________________________________________     Synthesis of Maleimides from Maleic Anhydride and an Amine                     R                 Procedure                                                                            Solvent                                                                             Temp (°C.)                                                                    Time (hrs)                                                                           Yield (%)                                                                            m.p. Appearance                 __________________________________________________________________________     Example 1                                                                            Dodecyl     A     MEK  60    22    96    92   Light brown powder         Example 2                                                                            2-Fluorophenyl                                                                             B     DMAc 23    24    64    55-59                                                                               Yellow crystals            Example 3                                                                            4-Fluorophenyl                                                                             B     DMAc 23    36    81    153-155                                                                             Yellow needles             Example 4                                                                            4-Chlorophenyl                                                                             B     DMAc 60    29    82    115-117                                                                             Yellow needles             Example 5                                                                            4-t-Butylphenyl                                                                            B     NMP  23    40    58    95-96                                                                               Yellow needles             Example 6                                                                            3-Trifluoromethylphenyl                                                                    B     DMF  50    48    41    oil  Orange                     Example 7                                                                            4-Trifluoromethylphenyl                                                                    B     DMAc 23    80    61    151-153                                                                             White                      __________________________________________________________________________                                                         powder                

Synthesis of Bisphenols ##STR11## Phenolphthaln (B)

To a 3L 3-necked flask containing 60 g of phenolphthalein (A), 450 mL of water and 525 mL of ethanol was added 450 mL of 50% sodium hydroxide solution in ethanol and 300 g of zinc powder. The contents were heated to reflux and maintained at that temperature for 12 hrs. The solution was cooled to room temperature, filtered and acidified until phenolphthalin precipitated as a white powder. This was collected by filtration and dried at 80° C. for 24 hrs. at reduced pressure. Yield=95%. m.p.=234-236° C.

Isobenzofuran (C)--Typical procedure

To a dry 250 mL round bottom flask equipped with a mechanical stirrer containing 20 g (0.062 mol) of phenolphthalin at 0° C. was added, with stirring, 25 mL of conc. sulfuric acid (cooled to 0° C.) This mixture was stirred slowly for 2-3 min. and poured into a 1L beaker containing 600 mL of ice-water. To retrieve the remaining solids there was added cold water (˜20-30 mL×4) while a spatula was used to scrape out the remainder. The solids were combined. The green solid was then filtered, washed with 1 L of cold water and dried for 15-20 min. before being used in the Diels-Alder reaction.

Bisaryl(imido)phenol (D)

To a 500 mL round bottom flask containing 0.069 mol N-(methyl) maleimide in 200 mL of absolute ethanol was added the isobenzofuran generated above. The mixture was heated to 80-90° C., After 15-20 min. the Diels-Alder reaction was complete as indicated by thin layer chromatography and a change in color from red and clear to light brown and clear. This product was not isolated, since the Diels-Alder reaction is accompanied by some dehydration which has already occurred due to the presence of residual sulfuric acid from the acid catalyzed rearrangement above.

To the mixture of products from the Diels-Alder reaction was added HCl(g), while maintaining the temperature at between 70-90° C. Complete dehydration usually occurred in about 1-2 hrs.

    ______________________________________                                         Bisphenols from Phenolphthalin                                                 R group         Yield   m.p.     Appearance                                    ______________________________________                                         Example 8                                                                              Dodecyl     50-60   255    Yellow needles                              Example 9                                                                              Methyl      50-60   410    Yellow needles                              Example 10                                                                             Phenyl      50-60   392    Yellow needles                              Example 11                                                                             2-Fluorophenyl                                                                             46      374-6  Yellow needles                              Example 12                                                                             4-Fluorophenyl                                                                             51      367    Yellow needles                              Example 13                                                                             4-Chlorophenyl                                                                             47      156-158                                                                               Yellow needles                              Example 14                                                                             3-Trifluoro-                                                                               62      362    Yellow needles                                      methylphenyl                                                           Example 15                                                                             4-Trifluoro-                                                                               43      360    Yellow powder                                       methylphenyl                                                           Example 16                                                                             2-Phenylphenyl                                                                             40      329-31 White crystals                              ______________________________________                                    

The precipitated product was filtered and dried. Yield=50-60%. ##STR12## Recrystallization from acetic acid yielded monomer pure enough for polymerization. When the electron withdrawing group on the ring is F or CF3 complete dehydration occurs by stirring overnight at 70-90° C., Hcl(g) is not required.

Polymer Synthesis Typical Procedure

To a dry 50 mL 3-neck flask equipped with a 2.5 cm Teflon stirring bar, a Dean-Stark trap (filled with toluene), a cold water condenser, a thermometer and nitrogen inlet was added 0.860 g (1.88 mmol) of N-Phenyl(imido)bisphenol and 0.605 g (1.88 mmol) of 1,3-bis(4-flurobenzoyl)benzene. 3.7 mL of toluene was used to wash down any remaining solids stuck to the mouth of the flask and 7.3 mL of NMP was added. The contents were warmed to 40° C. and 0.346 g (2.632 mmol-40% excess) of anhydrous potassium carbonate was added. The temperature was increased to reflux (130° C.). To insure complete dehydration refluxing was continued between 130° C. and 140° C. for two to three hours, at which time the temperature was slowly increased to 160-165° C. over about 3 hours (a significant increase in viscosity is apparent at 150° C.). Reaction at this temperature was continued until the reaction mixture could no longer be stirred or the polymer began to precipitate from solution. The reaction was diluted with 15-20 mL of NMP, filtered hot through Celite to remove the salts and precipitated dropwise into a vigorously stirred solution of methanol/water (300 mL : 200 mL, respectively). Filtration, drying, redissolved in 40 mL of chloroform and precipitation a second time in methanol yielded a white fibrous polymer after filtration. Drying at 80° C. under vacuum for 24 hours gave a 70% yield of white fibrous polymer.

    __________________________________________________________________________     PROPERTIES OF POLYMERS                                                                             Polymerization                                                                         Inherent  TGA (°C.)**                                                                             Young's Modulus          R                 X Solvent Viscosity                                                                           Tg (°C.)*                                                                    air N2 Solubility                                                                              at 23° C.                                                               (GPa)                    __________________________________________________________________________     Example 17                                                                           Methyl      B Sulfolane                                                                              --   283  525 516                                                                               Sulfolane                                                                               --                       Example 18        A Sulfolane                                                                              0.64 314  503 506                                                                               CHCl3 and TCE                                                                           2.5                      Example 19        C NMP     0.62 251  524 515                                                                               CHCL3    2.4                      Example 20                                                                           Dodecyl     B NMP     1.1  147  482 491                                                                               CHCL3/CH2CL2                                                                            2.6                      Example 21        A NMP     0.55 167  471 471                                                                               CHCL3/CH2CL2                                                                            2.6                      Example 22        C NMP     0.9  140  489 487                                                                               CHCL3/CH2CL2                                                                            2.7                      Example 23                                                                           Phenyl      B DMSO    0.52 275  551 561                                                                               CHCl3    2.5                      Example 24        A NMP     0.91 310  556 550                                                                               CHCL3 (hot)                                                                             2.6                      Example 25        C NMP     1.24 245  568 566                                                                               CHCL3/CH2CL2                                                                            2                        Example 26                                                                           4-Chlorophenyl                                                                             B NMP     0.71 272  550 564                                                                               CHCl3    2.8                      Example 27        A NMP     0.55 280  539 552                                                                               CHCl3    2.9                      Example 28                                                                           2-Phenylphenyl                                                                             A NMP     --   278  547 539                                                                               TCE      2                        Example 29                                                                           2-Fluorophenyl                                                                             B NMP     --   282  560 565                                                                               TCE      1.4                      Example 30        A NMP     --   --   549 540                                                                               TCE      3.4                      Example 31                                                                           4-Fluorophenyl                                                                             B NMP     1.07 290  560 578                                                                               NMP      0.8                      Example 32        A NMP     0.69 300  558 555                                                                               CHCl3    2.6                      Example 33        C NMP     0.71 243  572 572                                                                               CHCl3    2.8                      Example 34                                                                           3-Trifluoromethylphenyl                                                                    B NMP     0.65 252  561 569                                                                               TCE      3                        Example 35        A NMP     0.63 282  550 550                                                                               CHCl3    2.3                      Example 36                                                                           4-Trifluoromethylphenyl                                                                    B NMP     0.84 260  552 573                                                                               TCE      2                        Example 37        A NMP     0.56 290  540 542                                                                               CHCl3    1.7                      __________________________________________________________________________      *DSC                                                                           **Temperature for 10% weight loss                                        

Film Casting

Polymer films were cast from chloroform or sym-tetrachloroethane. For example, 130 mg of polymer was dissolved in 2-3 mL chloroform and evaporated slowly at room temperature (12-24 hours) to yield a tough and flexible film (Thickness=0.070-0.120 mm). For sym-tetrachloroethane, solutions were cast in a forced air oven at 108° C. (12-24 hours). 

We claim:
 1. A polymer of formula (II): ##STR13## in which R₁, R₂, R₃ and R₄, which may the same or different, are selected from the group consisting of hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, alkoxy of 1 to 6 carbon atoms and aryloxy of 6 to 10 carbon atoms;R₅ is selected from the group consisting of fluorine, chlorine, bromine and alkyl of 1 to 6 carbon atoms, m is 0, 1, 2, 3 or 4, R₇ is alkyl of 1 to 18 carbon atoms; aryl of 6 to 10 carbon atoms, unsubstituted or substituted one or more times by a substituent selected from the group consisting of fluorine, chlorine, trifluoromethyl alkyl of 1 to 6 carbon atoms and phenyl; or heteroaryl; X is --CO--, --SO₂ -- or --CO--Ar--CO-- in which Ar is phenylene, and n is an integer of 2 to
 200. 2. A polymer of claim 1 in which R₁, R₂, R₃ and R₄ are all hydrogen, m is 0; and X is --CO-- and para to the phenol oxygens of the polymer chain.
 3. A polymer of claim 2 in which R₇ is methyl, dodecyl, phenyl or phenyl substituted by fluoro, chloro, trifluoromethyl, t-butyl or phenyl.
 4. A polymer of claim 1, in which R₁, R₂, R₃ and R₄ are all hydrogen, m is 0, and X is --SO₂ -- and para to the phenolic oxygens of the polymer chain.
 5. A polymer of claim 4 in which R₇ is methyl, dodecyl, phenyl or phenyl substituted by fluoro, chloro, trifluoromethyl, t-butyl or phenyl.
 6. A polymer of claim 1 in which R₁, R₂, R₃ and R₄ are all hydrogen, m is 0; and X is -CO-Ar-CO wherein Ar is 1,3-phenylene.
 7. A polymer of claim 6 in which R₇ is methyl, dodecyl, phenyl or phenyl substituted by fluoro, chloro, trifluoromethyl, t-butyl or phenyl.
 8. A process for producing a polymer of formula (II): ##STR14## in which R₁, R₂, R₃ and R₄, which may be the same or different, are selected from the group consisting of hydrogen, fluorine chlorine, bromine, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, alkoxy of 1 to 6 carbon atoms and aryloxy of 6 to 10 carbon atoms;R₅ is selected from the group consisting of fluorine, chlorine, bromine and alkyl of 1 to 6 carbon atoms, m is 0, 1, 2, 3 or 4, R₇ is alkyl of 1 to 18 carbon atoms; aryl of 6 to 10 carbon atoms, unsubstituted or substituted one or more times by a substituent selected from the group consisting of fluorine, chlorine, trifluoromethyl alkyl of 1 to 6 carbon atoms and phenyl; or heteroaryl; X is --CO--, --SO₂ -- or --CO--Ar--CO-- in which Ar is phenylene, and n is an integer of 2 to 200; comprising polymerizing a bisphenol of formula (I): wherein said polymerizing is carried out at 160 to 180 C. in a solvent in the presence of anhydrous potassium carbonate. ##STR15## in which R₁ to R₅, R₇ and m are as defined above, with a compound of formula (XII): ##STR16## in which Y is fluoro or chloro, and X is --CO--, --SO₂ -- or ##STR17##
 9. A process according to claim 8 in which said compound of formula (XII) is 4,4'-difluorobenzophenone.
 10. A process according to claim 8 in which said compound of formula (XII) is 4,4'-difluorodiphenyl sulfone.
 11. A process according to claim 8 in which said compound of formula (XII) is 1,3-bis-(4-fluorobenzoyl)benzene.
 12. A process according to claim 9 in which R₁, R₂, R₃ and R₄ are all hydrogen, and m is
 0. 13. A process according to claim 10 in which R₁, R₂, R₃ and R₄ are all hydrogen, and m is
 0. 14. A process according to claim 11 in which R₁, R₂, R₃ and R₄ are all hydrogen, and m is
 0. 